KR101890915B1 - Polyarylene sulfide resin composition and formed article - Google Patents

Abstract

The present invention relates to a polyarylene sulfide resin composition and a molded article, which have improved compatibility with other polymer materials and fillers and exhibit mechanical properties such as excellent tensile strength or impact strength with higher thermal conductivity. Such a polyarylene sulfide resin composition includes polyarylene sulfide, expandable graphite; Boron nitride; And an inorganic filler containing at least one selected from the group consisting of zinc sulfide, magnesium oxide and zinc oxide.

Description

[0001] POLYARYLENE SULFIDE RESIN COMPOSITION AND FORMED ARTICLE [0002]

The present invention relates to a polyarylene sulfide resin composition and a molded article, which have improved compatibility with other polymer materials and fillers and exhibit mechanical properties such as excellent tensile strength or impact strength with higher thermal conductivity.

Polyarylene sulfide is a typical engineering plastic. It is used for various products and electronic products used in high temperature and corrosive environment due to high heat resistance, chemical resistance, flame resistance and electric insulation. Demand is increasing.

Of these polyarylene sulfides, polyphenylene sulfide (PPS) is currently commercially available. The commercial production process of PPS, which is mainly applied up to now, is a process in which p-dichlorobenzene (pDCB) and sodium sulfide are used as raw materials and N-methyl pyrrolidone In a polar organic solvent. This method is known as the Macallum process.

However, the polyarylene sulfide produced by such a solution-polymerized Mcarray process has a disadvantage in that mechanical properties such as tensile strength are poor at high temperature and productivity thereof is not excellent.

Accordingly, there has been proposed a process for producing a polyarylene sulfide such as PPS by melt polymerization of a reaction product containing a diiodo aromatic compound and a sulfur element. The polyarylene sulfide thus produced has excellent mechanical properties even at a high temperature, does not require the use of an organic solvent, and has an excellent productivity.

However, in the case of the polyarylene sulfide produced by the melt polymerization method, the end of its main chain is composed of iodine and most of the aryl groups (typically, benzene). In the case of such polyarylene sulfide, due to the nature of the main chain structure, compatibility with other reinforcing materials or fillers such as other polymer materials or glass fibers is poor.

Therefore, in the case of the polyarylene sulfide produced by the melt polymerization method, it is difficult to compound with other polymer materials or fillers in order to exhibit optimized physical properties suitable for various uses, and even when compounding, There was a disadvantage that it was difficult to bet. Due to these problems, it has been found that the previously known polyarylene sulfide resin composition has difficulty exhibiting sufficient physical properties suitable for each application and has limitations in application to various applications.

On the other hand, recent high-density packaging and functionalization of electronic materials and devices has led to internal temperature rise by heat-generating parts inside the product, and problems such as speed reduction of electronic parts due to temperature rise Accordingly, development of a highly heat-resistant plastic having an insulation property of 5 W / mK or more is required.

Although a variety of thermally conductive plastics have been known to be applicable to such high heat-dissipating plastics in the past, the addition of a relatively large amount of inorganic filler has made it possible to develop the thermal conductivity required in the industry. When such a large amount of inorganic filler is used, Mechanical properties, formability, and economy are deteriorated.

Accordingly, there is a continuing demand for a plastic heat-dissipating material that overcomes the disadvantages of the conventional thermally conductive plastic and can exhibit excellent thermal conductivity even with a small use amount of the inorganic filler, thereby exhibiting and maintaining excellent mechanical properties.

The present invention provides a polyarylene sulfide-based resin composition which has improved compatibility with other polymer materials and fillers, and exhibits mechanical properties such as excellent tensile strength or impact strength with higher thermal conductivity.

In addition, the present invention provides a molded article including the polyarylene sulfide resin composition and exhibiting properties optimized for each use.

The present invention relates to polyarylene sulfide and expandable graphite; Boron nitride; And an inorganic filler containing at least one selected from the group consisting of zinc sulfide, magnesium oxide, and zinc oxide.

The present invention also provides a molded article comprising the polyarylene sulfide resin composition.

Hereinafter, a polyarylene sulfide resin composition and a molded article including the polyarylene sulfide resin composition according to a specific embodiment of the present invention will be described. It is to be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

&Quot; Including "or" containing ", unless the context clearly dictates otherwise throughout the specification, refers to any element (or component) including without limitation, excluding the addition of another component .

According to one embodiment of the invention, there is provided a process for producing a polyarylene sulfide, an expandable graphite; Boron nitride; And an inorganic filler containing at least one selected from the group consisting of zinc sulfide, magnesium oxide, and zinc oxide.

The present inventors have found that the above expanded graphite; Boron nitride; And a polyarylene sulfide resin composition which exhibits excellent thermal conductivity while using a relatively small amount of an inorganic filler by mixing three kinds of inorganic fillers of zinc sulfide, magnesium oxide or zinc oxide with polyarylene sulfide , And completed the invention. Such a resin composition can exhibit excellent thermal conductivity while exhibiting excellent thermal conductivity while relatively reducing the amount of inorganic filler used, and can exhibit excellent mechanical properties peculiar to polyarylene sulfide. In accordance with the demand of the related art, plastic resin materials And the like.

In the resin composition of one embodiment, the polyarylene sulfide may have a reactive group such as a carboxyl group (-COOH) or an amine group (-NH ₂ ) introduced into at least a part of the end group of the main chain. The reactive group introduced polyarylene sulfide may exhibit higher compatibility with other components as well as the inorganic filler. Therefore, due to the use of the reactive group-introduced polyarylene sulfide, the resin composition of one embodiment not only exhibits improved thermal conductivity and mechanical properties, but also has a synergistic effect through compounding with various other materials Lt; / RTI >

The excellent compatibility with the introduction of such reactive groups can be expected to be due to the following technical principles.

In the case of the polyarylene sulfide previously prepared by the melt polymerization method, since the main chain terminal thereof is composed of iodine and most of the aryl groups (typically, benzene), substantially no reactive groups are present at the end of the main chain. Therefore, the polyarylene sulfide is disadvantageous in that it is inferior in compatibility with fillers including various reinforcing materials such as other polymer materials or glass fibers, and inorganic fillers.

In contrast, in the case of a polyarylene sulfide in which a reactive group such as a carboxyl group (-COOH) or an amine group (-NH ₂ ) is introduced into at least a part of the main chain terminal, the presence of the reactive group causes the presence of other polymer materials, It has been confirmed that it exhibits excellent compatibility with an inorganic filler and the like for the improvement of the strength. As a result, when the resin composition of one embodiment contains the inorganic filler described above together with the polyarylene sulfide, it exhibits excellent heat resistance, chemical resistance, and excellent mechanical properties peculiar to polyarylene sulfide, The increase in physical properties due to mixing with the material (for example, compounding) can be optimized to exhibit more improved thermal conductivity and mechanical properties, and furthermore, it is possible to exhibit excellent physical properties suitable for various applications through mixing with other components Thereby enabling the provision of a molded article.

In the resin composition of this embodiment, the reactive group-introduced polyarylene sulfide has a peak or amine at about 1600 to 1800 cm < ^-1 > derived from the carboxy group at the end of the main chain in the FT-IR spectrum when analyzed by FT-IR spectroscopy From about 3300 to 3500 cm <& quot ^{; 1} > The intensity of each of these peaks can correspond to the content of each reactive group bonded to the main chain terminal group.

The In one embodiment, the carboxyl group or an amine group introduced polyarylene sulfide is on the FT-IR spectrum, when a high intensity of Ring stretch peak appearing at about 1500 to 1600cm ^-1 to 100%, wherein approximately 1600 to 1800cm ^{- 1} or about 0.001 to 10%, or about 0.01 to 7%, or about 0,1 to 4%, or about 0.5 to 3.5%, of the relative height intensity of the peak at about 3300 to 3500 cm ^-1 . At this time, the ring stretch peak appearing at 1500 to 1600 cm ^-1 may be derived from an arylene group such as phenylene contained in the main chain of the polyarylene sulfide. A peak of about 3300 to 3500 cm ^-1 derived from a peak or an amine group at about 1600 to 1800 cm ^-1 derived from the carboxyl group is in the range described above with respect to the height intensity of a peak derived from an arylene group (for example, a phenylene group) The polyarylene sulfide contained in the resin composition of one embodiment exhibits superior compatibility with fillers including other polymer materials or inorganic fillers and can maintain excellent physical properties unique to polyarylene sulfide . Therefore, the resin composition according to one embodiment of the present invention can exhibit better thermal conductivity and mechanical properties as a result of mixing with a predetermined inorganic filler, and further, can exhibit a superior synergistic effect due to the compounding of other polymer materials or fillers .

On the other hand, the above-mentioned polyarylene sulfide may contain a disulfide repeating unit in the repeating unit of the main chain. Here, the disulfide repeating unit refers to a repeating unit of the polyarylene sulfide represented by the following general formula (1) wherein a polyarylene disulfide repeating unit of the general formula (2) containing a disulfide bond (-SS-bond) You can refer to:

[Formula 1]

[Formula 2]

In the general formulas 1 and 2, Ar represents a substituted or unsubstituted arylene group.

As described above, since the polyarylene sulfide contained in the resin composition of one embodiment includes the disulfide repeating unit, it is possible to inhibit the polyarylene sulfide from including an oligomer-form polymer chain having an excessively low molecular weight in an equivalent amount . This is because the disulfide bond in the disulfide repeating unit continuously causes a sulfur exchange reaction between the polymer chains contained in the polyarylene sulfide, and the molecular weight of the polymer chains contained in the polyarylene sulfide can be substantially uniformed. As a result, the polyarylene sulfide contained in the resin composition of one embodiment can contain an oligomer-type polymer chain having an excessively low molecular weight in a minimum amount, and the molecular weight distribution of the entire polymer chains becomes uniform so that the molecular weight distribution curve is relatively narrow It can be derived as a symmetric shape close to a normal distribution curve. Therefore, the resin composition of one embodiment including such a polyarylene sulfide can significantly reduce the amount of flashes generated, and exhibit improved processability, even when a product requiring high precision is molded.

Such disulfide repeating units may be included in an amount of about 3 wt% or less, or about 0.01 to 3.0 wt%, or about 0.1 to 2.0 wt%, based on the total polyarylene sulfide. As a result, the workability improving effect due to the disulfide repeating unit can be optimized, and the disulfide repeating unit is excessively increased, so that the physical properties of the polyarylene sulfide can be prevented from being lowered.

On the other hand, the polyarylene sulfide contained in the resin composition of one embodiment may have a melting point of about 265 to 290 ° C, or about 270 to 285 ° C, or about 275 to 283 ° C. With such a melting point range, the polyarylene sulfide obtained by a melt polymerization method and a resin composition of one embodiment containing the reactive group introduced with a reactive group can exhibit excellent heat resistance and flame retardancy.

The polyarylene sulfide may have a number average molecular weight of about 5,000 to 50,000, or about 8,000 to 40,000, or about 10,000 to 30,000. The polyarylene sulfide may have a degree of dispersion of about 2.0 to 4.5, or about 2.0 to 4.0, or about 2.0 to 3.5, which is defined as a weight average molecular weight based on the number average molecular weight. As the polyarylene sulfide has a degree of dispersion and a molecular weight in the above-mentioned range, the resin composition of one embodiment containing the polyarylene sulfide can exhibit excellent mechanical properties and processability, and can be processed into various molded articles .

The above-mentioned polyarylene sulfide may have a melt viscosity of about 10 to 50,000 poise, or about 1,00 to 20,000, or about 3,000 to 10,000 as measured by a rotating disk viscometer at 300 ° C. The polyarylene sulfide exhibiting such a melt viscosity and the resin composition of one embodiment containing the polyarylene sulfide can exhibit excellent processability and excellent mechanical properties.

For example, the polyarylene sulfide included in the resin composition of one embodiment has a tensile strength value measured according to ASTM D 638 of about 100 to 900 kgf / cm ² , or about 200 to 800 kgf / cm ² , or about 300 To 700 kgf / cm < ² >, and may have an elongation of about 1 to 10%, or about 1 to 8%, or about 1 to 6%, measured according to ASTM D 638. The polyarylene sulfide may have a flexural strength value measured according to ASTM D 790 of about 100 to 2000 kgf / cm ² , or about 500 to 2000 kgf / cm ² , or about 1000 to 2000 kgf / cm ² , And the impact strength measured according to ASTM D 256 may be about 1 to 100 J / m, or about 5 to 50 J / m, or about 10 to 20 J / m. As described above, the polyarylene sulfide contained in the resin composition of one embodiment can exhibit various physical properties such as excellent mechanical properties, and can exhibit excellent compatibility with fillers including other polymer materials or inorganic fillers, The resin composition of one embodiment may exhibit higher synergistic effect depending on mixing of each component and excellent physical properties suitable for various uses.

On the other hand, the resin composition of one embodiment may contain, together with the above-described polyarylene sulfide, a predetermined inorganic filler, for example, expandable graphite; Boron nitride; And at least three kinds of inorganic fillers composed of at least one selected from the group consisting of zinc sulfide, magnesium oxide and zinc oxide. In the resin composition of one embodiment, these three kinds of inorganic fillers may exist dispersed in a form that is structurally connected to each other in surface contact with each other in polyarylene sulfide as a polymer matrix. Due to the interaction of these three kinds of inorganic fillers, the resin composition of one embodiment can exhibit higher thermal conductivity, and it is possible to use a relatively small amount of inorganic filler, so that excellent mechanical properties and the like can be expressed and maintained .

In addition, the inorganic filler may be contained in a state without being subjected to a separate surface treatment, but at least one or more inorganic fillers, for example, boron nitride may be included in a state where the surface is subjected to organic coating treatment. The organic coating treatment of such an inorganic filler can be carried out by any method well known to those skilled in the art and can be carried out by, for example, stearic acid, organic titanate, organic zirconate or polydimethylsiloxane, Coating treatment can be performed.

The inclusion of the inorganic filler thus treated can further improve the substantial contact area, affinity and compatibility with the polymer matrix containing the inorganic filler and the polyarylene sulfide. As a result, the thermal conductivity of the resin composition of one embodiment And physical properties can be more optimized.

Among the three kinds of inorganic fillers, expandable graphite having an average particle diameter of 1 to 1000 μm and an aspect ratio of 50 or more can be used. This expanded graphite may be obtained by physically and chemically separating natural graphite, and the crystal structure may be hexagonal. In the resin composition, two or more kinds of expanded graphite having different flatness ratios or average particle sizes may be mixed and used. It has been confirmed that the thermal conductivity and other physical properties of the resin composition of one embodiment are significantly lowered when the expanded graphite and other types of natural graphite or the like are used.

The boron nitride may have an average particle diameter of 5 to 1000 μm and an aspect ratio of 50 to 300, and the crystal structure may be hexagonal. In the resin composition, two or more kinds of boron nitride having different average particle diameters may be mixed and used. According to the mixed use of the boron nitride, the packing density of the inorganic filler is more optimized, so that the resin composition of one embodiment can exhibit improved thermal conductivity.

In one embodiment, the resin composition may include at least one of zinc sulfide, magnesium oxide, and zinc oxide. The zinc sulfide may have a specific surface area of 50 to 300 m ² / g, blende structure. The magnesium oxide may suitably have a purity of about 97% or more, an average particle size of about 3 to 5 μm, a specific surface area of about 30 to 200 m ² / g, or about 30 to 100 m ² / g. In order to suppress the reaction of magnesium oxide in air, it can be used in a surface coated form. The zinc oxide may have a purity of about 99% or more, an average particle size of about 0.3 to 0.8 μm, a specific surface area of about 3 to 7 m ² / g, or about 3.5 to 6 m ² / g.

In the resin composition, two or more of these components may be used, or two or more components having different specific surface areas may be mixed and used as respective components.

On the other hand, the above-mentioned polyarylene sulfide resin composition comprises 10 to 80% by weight of polyarylene sulfide, 1 to 50% by weight of expanded graphite, 1 to 50% by weight of boron nitride, and zinc sulfide, magnesium oxide and zinc oxide And 1 to 50% by weight of at least one selected from the group consisting of By including each component in such a content range, the resin composition of one embodiment can exhibit superior thermal conductivity and mechanical properties due to mixing with a predetermined inorganic filler while maintaining excellent physical properties peculiar to polyarylene sulfide.

On the other hand, it is already described that the polyarylene sulfide included in the resin composition of one embodiment, for example, the polyarylene sulfide into which the reactive group is introduced, can exhibit excellent compatibility with various other polymer materials and fillers. Accordingly, the resin composition of one embodiment may be mixed (e.g., compounded) with various other polymer materials or fillers to exhibit an excellent synergistic effect and exhibit optimized properties for various applications.

Thus, the resin composition of one embodiment may include other polymeric materials such as thermoplastic resin or thermoplastic elastomer, filler, etc. in addition to the above-mentioned components. Examples of the polymer material that can be included in the resin composition of one embodiment include various thermoplastic resins such as a polyvinyl alcohol resin, a vinyl chloride resin, a polyamide resin, a polyolefin resin or a polyester resin; And various thermoplastic elastomers such as polyvinyl chloride elastomer, polyolefin elastomer, polyurethane elastomer, polyester elastomer, polyamide elastomer or polybutadiene elastomer.

The filler that may be included in the resin composition in addition to the predetermined inorganic filler may be an organic or inorganic filler in the form of fiber, bead, flake, or powder, and specific examples thereof include glass fiber, carbon fiber, boron fiber , Glass beads, glass flakes, talc or calcium carbonate.

As a typical example of such a filler, glass fiber can be exemplified. By adding such glass fiber, the mechanical properties of the resin composition and the molded article of one embodiment can be reinforced. The surface of the glass fiber may be treated with a silane coupling agent or the like or may be used in an untreated form. However, the cohesive force or compatibility of the filler and the polyarylene sulfide may be further improved during surface treatment with a silane coupling agent. The glass fiber may have an average particle diameter of 2 to 5 mm and a thickness of 10 to 15 占 퐉. The content of the glass fiber in the resin composition may be 1 to 50% by weight.

In addition to the above-mentioned respective components, the resin composition of one embodiment may further include a compatibilizer to further improve the compatibility of the polyarylene sulfide with the inorganic filler and the interfacial adhesion. Examples of such compatibilizers include silane compounds, maleic anhydride, titanate, zirconate, fumaric acid, phosphate, stearic acid, , Metal stearate or wax, and mixtures of two or more selected from these may be used. Such a compatibilizing agent may further comprise 0.1 to 20% by weight of the resin composition.

For reference, in the resin composition of one embodiment, each inorganic filler needs to be evenly dispersed in a matrix containing polyarylene sulfide, and structurally and organically connected to each other in surface contact with each other. If these requirements are met, the resin composition of one embodiment can exhibit improved thermal conductivity due to the connection and synergism between each inorganic filler. To this end, the compatibilizer may further be included, whereby the resin composition of one embodiment may exhibit improved thermal conductivity and mechanical properties.

On the other hand, when a higher thermal conductivity is desired in the production of the resin composition of one embodiment, it may be necessary to add a larger amount of inorganic filler. In this case, a separate feeding device for feeding the inorganic filler may be used.

In addition, the resin composition of one embodiment may further include additional additives and / or stabilizers to further improve the mechanical properties, heat resistance, weather resistance, or moldability. Examples of such additives include, but are not limited to, an oxidation stabilizer, a light stabilizer (UV stabilizer and the like), a plasticizer, a lubricant, a nucleating agent or an impact reinforcement. You may.

Among these additives, a primary or secondary antioxidant may be used as the oxidation stabilizer, and more specific examples thereof include hindered phenol-based, amine-based, sulfur-based or phosphorus-based antioxidants. In addition, the light stabilizer may be included when the resin composition of one embodiment is applied to an exterior material. In particular, a UV stabilizer is typically used, and examples thereof include benzotriazole and benzophenol.

The lubricant is a component used for improving the moldability in molding and processing the resin composition of one embodiment, and a hydrocarbon-based lubricant can be typically used. By using such a lubricant, it is possible to impart releasability such as prevention of friction between the resin composition and the metal mold and desorption in the mold.

In addition, various nucleating agents can be used to improve the crystallization speed during the molding process of the resin composition, and it is possible to improve the solidification speed of the product upon compression, injection, and shorten the cycle time of the product.

In addition to the above-mentioned polymer materials, fillers or additives, various other polymer materials, reinforcements / fillers or additives, etc. may be included in the resin composition of one embodiment together with the above-mentioned polyarylene sulfide to exhibit more excellent properties Of course. More specifically, various polymer materials or fillers for further improving the mechanical properties, heat resistance, weather resistance or moldability of the resin composition can be included in the resin composition of one embodiment without limitation.

Meanwhile, the resin composition of one embodiment may include a melt-polymerization type polyarylene sulfide in which a reactive group such as a carboxyl group (-COOH) or an amine group (-NH ₂ ) is introduced at the main chain terminal as a main resin component. Such polyarylene sulfide can be obtained, for example, by polymerizing a reactant comprising a diiodo aromatic compound and a sulfur element; And a step of further adding a compound having a reactive group of a carboxyl group or an amine group, while proceeding to the polymerization reaction step. In order to adjust the content of the disulfide repeating unit contained in the polyarylene sulfide to an appropriate range, it is preferable that, for example, in the course of the polymerization reaction step, 0.01 to 10 parts by weight, And further adding 30 parts by weight of a sulfur element.

Hereinafter, a method for producing such polyarylene sulfide will be described.

In the method for producing polyarylene sulfide, the polymerization reaction between the diiodo aromatic compound and the sulfur element is about 90% when the progress of the polymerization reaction is measured at a ratio of the present viscosity to the target viscosity, , Or from about 90% to less than 100% (for example, at a later stage of the polymerization reaction). The degree of progress of the polymerization reaction is determined by setting the molecular weight of the polyarylene sulfide to be obtained and the target viscosity of the resulting polymerization product and measuring the present viscosity according to the progress of the polymerization reaction to determine the ratio of the present viscosity to the target viscosity Can be measured. At this time, the method of measuring the present viscosity can be determined by a method which is obvious to a person skilled in the art according to the reactor scale. For example, when polymerization proceeds in a relatively small polymerization reactor, a sample undergoing polymerization in the reactor can be taken and measured with a viscometer. Alternatively, when polymerization is carried out in a large continuous polymerization reactor, the present viscosity can be automatically measured continuously and in real time by a viscometer installed in the reactor itself.

As described above, in the course of the polymerization reaction of the reaction product comprising the diiodo aromatic compound and the sulfur element, a compound having a reactive group of a carboxyl group or an amine group is added at the latter stage of the polymerization reaction and reacted to produce a polyarylene sulfide main chain A molten polymerizable polyarylene sulfide having such a reactive group introduced into at least a part of the end group can be produced. Particularly, a compound having a reactive group is further added to the latter stage of the polymerization reaction to introduce a reactive group having an appropriate amount into the terminal group of the main chain, thereby exhibiting excellent compatibility with the above-mentioned other polymer material or filler including a predetermined inorganic filler, The polyarylene sulfide of one embodiment having excellent physical properties peculiar to polyarylene sulfide can be effectively produced.

In the method for producing polyarylene sulfide, as the compound having a carboxyl group or an amine group, a compound in the form of any monomer (monomolecular) having a carboxyl group or an amine group can be used. More specific examples of such a compound having a carboxyl group or an amine group include 2-iodobenzoic acid, 3-iodobenzoic acid, 4-iodobenzoic acid, 2,2-iodobenzoic acid, 2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 2,2'-dithiobenzoic acid, Dithiodianiline, and 4,4'-dithiodianiline. In addition, compounds having various carboxyl groups or amine groups can be used.

The compound having a reactive group may be added in an amount of about 0.0001 to 5 parts by weight, or about 0.001 to 3 parts by weight, or about 0.01 to 2 parts by weight based on about 100 parts by weight of the diiodinated aromatic compound. With such a content, it is possible to add a compound having a reactive group to introduce an appropriate amount of a reactive group into the terminal group of the main chain. As a result, it is possible to obtain a polyarylene sulfide A polyarylene sulfide having unique excellent physical properties can be effectively produced.

In addition, the polyarylene sulfide described above is prepared by a method of polymerizing a reaction product containing a diiodo aromatic compound and a sulfur element, thereby exhibiting excellent mechanical properties and the like as compared with those produced by a conventional M-column process .

The diiodoaromatic compounds usable for the polymerization include diiodobenzene (DIB), diiodonaphthalene, diiodobiphenyl, diiodobisphenol, and benzodiophene diiodide (diiodobenzophenone). However, the present invention is not limited to this, and an alkyl group, a sulfone group, or the like may be bonded to such a compound by a substituent, Or a diiodoaromatic compound containing an atom such as nitrogen may also be used. The diiodoaromatic compounds include isomers of various diiodide compounds depending on positions where iodine atoms are attached. Among them, para-diiodobenzene (pDIB), 2,6-diiodonaphthalene, or p, a compound in which iodine is bonded to a para position like p'-diiodobiphenyl can be more suitably used.

There is no particular limitation on the form of the sulfur element reacting with the diiodoaromatic compound. Normally, the sulfur element exists in cyclooctasulfur (S8) in which eight atoms are connected at room temperature. If sulfur is not commercially available, it can be used in any solid or liquid state.

Further, as already mentioned above, in order to adjust the content of the disulfide repeating units contained in the above-mentioned polyarylene sulfide to a suitable range of, for example, about 3% by weight or less, the sulfur element is additionally added . The amount of the sulfur element to be additionally added may be appropriately determined by those skilled in the art in consideration of the content of the appropriate disulfide repeating unit. For example, the sulfur element may be added in an amount of 0.01 to 30 parts by weight based on 100 parts by weight of the sulfur element contained in the initial reaction . The additionally added sulfur element may be added, for example, when the polymerization reaction proceeds by about 50 to 99%, and may be added separately or added to the compound already having the above-mentioned reactive group.

The reaction product for the production of the polyarylene sulfide may further contain a polymerization initiator, a stabilizer, or a mixture thereof in addition to the diiodide aromatic compound and the sulfur element. Specific examples of usable polymerization initiators include 1,3- At least one member selected from the group consisting of diiodo-4-nitrobenzene, mercaptobenzothiazole, 2,2'-dithiobenzothiazole, cyclohexylbenzothiazole sulfenamide, and butylbenzothiazole sulfenamide But it is not limited to the above example.

The constitution of the stabilizer is not particularly limited as long as it is a stabilizer usually used in the polymerization reaction of the resin.

On the other hand, during the polymerization reaction as described above, the polymerization terminator may be added at a point of time when polymerization has been carried out to some extent. The composition of the polymerization terminator is not limited as long as it is a compound capable of stopping the polymerization by removing the iodine group contained in the polymer to be polymerized. Specific examples thereof include diphenyl suldifide, diphenyl ether, diphenyl, benzophenone, dibenzothiazole disulfide, monoiodoaryl compound, At least one member selected from the group consisting of benzothiazoles, benzothiazolesulfenamides, thiurams, dithiocarbamates and diphenyl disulfides can be used .

More preferably, the polymerization terminator is selected from the group consisting of iodobiphenyl, iodophenol, iodoaniline, iodobenzophenone, 2-mercaptobenzothiazole, ), 2,2'-dithiobisbenzothiazole, N-cyclohexylbenzothiazole-2-sulfenamide, 2-morpholinothiobenzo But are not limited to, 2-morpholinothiobenzothiazole, N, N-dicyclohexylbenzothiazole-2-sulfenamide, tetramethylthiuram monosulfide, May be at least one member selected from the group consisting of tetramethylthiuram disulfide, Zinc dimethyldithiocarbamate, Zinc diethyldithiocarbamate, and diphenyl disulfide .

On the other hand, the timing of administration of the polymerization terminator can be determined in consideration of the molecular weight of the polyarylene sulfide to be finally polymerized. For example, the diiodo aromatic compound contained in the initial reaction may be administered at a time when about 70 to 100% by weight of the diiodide aromatic compound has reacted and is exhausted.

The polymerization reaction as described above can be carried out under any condition so long as the polymerization of the reaction product containing the diiodo aromatic compound and the sulfur element can be initiated. For example, the polymerization can be carried out under reduced pressure, in which case temperature rises and pressure drops are carried out under initial reaction conditions of a temperature of about 180 to 250 ° C. and a pressure of about 50 to 450 torr, At a temperature of about 270 to 350 DEG C and a pressure of about 0.001 to 20 torr, and may be carried out for about 1 to 30 hours. As a more specific example, the polymerization can be carried out at a temperature of about 280 to 300 DEG C and a pressure of about 0.1 to 0.5 torr as a final reaction condition.

Meanwhile, the method for producing polyarylene sulfide may further include a step of melt-mixing a reaction product containing a diiodo aromatic compound and a sulfur element before the polymerization reaction. Such a melt mixing can be carried out at a temperature of, for example, about 130 캜 to 200 캜, or about 160 캜 to 190 캜, although the constitution is not limited as long as all of the above-mentioned reactants can be melt-mixed.

As described above, the melt-mixing step is carried out before the polymerization reaction, and the polymerization reaction to be carried out at a later stage can be proceeded more easily.

And, in the above-mentioned method for producing polyarylene sulfide, the polymerization reaction can be carried out in the presence of a nitrobenzene-based catalyst. Further, when the melt-mixing step is carried out before the polymerization reaction as described above, the catalyst may be added in the melt-mixing step. Examples of the nitrobenzene-based catalyst include 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, and the like, but the present invention is not limited thereto.

The melt-polymerization type polyarylene sulfide in which a predetermined reactive group is introduced at the end of the main chain can be obtained by the above-described production method, and the polyarylene sulfide exhibits excellent compatibility with filler such as another polymer material or inorganic filler Accordingly, it is possible to obtain a resin composition of one embodiment exhibiting various physical properties including excellent thermal conductivity and mechanical properties by using the same.

According to another embodiment of the present invention, there is provided a molded article comprising the polyarylene sulfide resin composition of one embodiment described above and a method for producing the same. The molded article may be manufactured by a method including a step of extruding the resin composition of one embodiment.

Hereinafter, the molded article and the manufacturing method will be described in more detail. However, the types and contents of the components that can be contained in the molded article have already been described with respect to the resin composition of one embodiment, and a further detailed description thereof will be omitted.

The molded article of another embodiment optionally contains a melt-polymerization type polyarylene sulfide, a predetermined inorganic filler, and optionally other additives, into which a predetermined reactive group has been introduced. These components are mixed to obtain a resin composition of one embodiment And then extruding it.

For example, a twin-screw extruder can be used to produce a molded article by mixing and extruding the resin composition containing the above-mentioned respective components. The ratio (L / D) About 30 to about 50 can be.

According to one example, first, a small amount of other additive or the like may be mixed with polyarylene sulfide in advance by a mixer such as a super mixer, and the premixed primary composition may be introduced through the main inlet of the twin screw extruder . In addition, a predetermined inorganic filler or the like can be separately introduced through a side feeder located on the side of the extruder. At this time, the position at which the side is injected may be about 1/3 to 1/2 point from the outlet side of the entire barrel of the extruder. By doing so, it is possible to prevent the inorganic filler or the like from being broken in the extruder by rotation and friction caused by the extruder screw.

In this manner, the respective components of the resin composition of one embodiment are mixed and extruded by a twin-screw extruder to obtain molded articles of other embodiments.

The molded articles of this alternative embodiment may be in various forms such as films, sheets, or fibers. The molded article may be an injection molded article, an extrusion molded article, or a blow molded article. From the viewpoint of crystallization, the mold temperature in the case of injection molding can be at least about 50 DEG C, at least about 60 DEG C, or at least about 80 DEG C, and from the viewpoint of deformation of the test piece, about 190 DEG C or less, Or about 160 캜 or less.

When the molded product is in the form of a film or a sheet, it can be made into various films or sheets such as unstretched, uniaxially stretched, and biaxially stretched. The fiber can be used as a fabric, a knitted fabric, a nonwoven fabric (spun bond, melt blow, staple), a rope, or a net made of various fibers such as undrawn yarn, drawn yarn or primary yarn.

Such molded articles can be used as coatings for electrical and electronic parts such as computer accessories, architectural members, automobile parts, machine parts, daily products or chemical parts, and industrial chemical resistant fibers. Particularly, since the molded article can exhibit better thermal conductivity and mechanical properties, it can be suitably applied as a highly heat-dissipating plastic applied to electronic products and the like.

In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.

The present invention provides a polyarylene sulfide resin composition having improved compatibility with other polymer materials and fillers and exhibiting mechanical properties such as excellent tensile strength or impact strength with higher thermal conductivity and a resin molded article produced therefrom can do.

These resin compositions can be suitably applied as highly heat-dissipating plastics for electronic products, and can exhibit excellent physical properties optimized for each application including them, and exhibit excellent physical properties unique to polyarylene sulfide. This is because the compatibility of each component of the resin composition is improved and the physical properties of each component can exhibit a synergistic effect.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Synthetic example  One: Carboxy group  or Amine group Backbone  Terminal Polyarylene Sulfide  synthesis

A thermocouple capable of measuring the inner temperature of the reactor and a 5 L reactor equipped with a vacuum line capable of charging nitrogen and vacuum were charged with 5130 g of para-iodobenzene (p-DIB), 450 g of sulfur, 1,3-diiodo- The reaction mixture containing 4 g of 4-nitrobenzene was heated to 180 ° C. and completely melted and mixed. Then, starting from the initial reaction conditions of 220 ° C. and 350 Torr, the final reaction temperature was 300 ° C., the pressure was gradually increased to 1 Torr, The polymerization reaction was carried out while performing the pressure drop. The progress of the polymerization reaction was measured as a relative ratio of the present viscosity to the target viscosity in the form of "(current viscosity / target point degree) * 100%" when the polymerization reaction progressed by 80% Was measured by a viscometer), 25 g of 2,2'-dithiobisbenzotriazole as a polymerization terminator was added, and the reaction was allowed to proceed for 1 hour. Then, 51% of 4-Iodoaniline was added to the reaction mixture, and the mixture was reacted under nitrogen atmosphere for 10 minutes. Subsequently, the reaction was continued for 1 hour under a vacuum of 0.5 Torr or less, Or a polyarylene sulfide resin containing an amine group at the main chain terminal was synthesized. The resin after completion of the reaction was prepared in the form of pellets using a small strand cutter.

On spectrum analyzes the polyarylene sulfide resin of this Synthesis Example 1 by FT-IR, from about 3300 to 3500cm ^- it was confirmed the presence of the amine groups of the ^first peak. Further, the FT-IR spectrum on, when a high intensity of Ring stretch peak appearing at about 1500 to 1600cm ^-1 to 100%, the relative height of the peak intensity of about 3300 to 3500cm ^-1 was confirmed to be about 1.4%.

Synthetic example  2: Carboxy group  or Amine group  Do not have Polyarylene Sulfide  synthesis

A thermocouple capable of measuring the inner temperature of the reactor and a 5 L reactor equipped with a vacuum line capable of charging nitrogen and vacuum were charged with 5130 g of para-iodobenzene (p-DIB), 450 g of sulfur, 1,3-diiodo- The reaction mixture containing 4 g of 4-nitrobenzene was heated to 180 ° C. and completely melted and mixed. Then, starting from the initial reaction conditions of 220 ° C. and 350 Torr, the final reaction temperature was 300 ° C., the pressure was gradually increased to 1 Torr, The polymerization reaction was carried out while performing the pressure drop. The degree of progress of the polymerization reaction was measured as the relative ratio of the present viscosity to the target viscosity in the formula of "(current viscosity / target point degree) * 100%" when the polymerization reaction proceeded at 80% 25 g of 2,2'-dithiobisbenzotriazole was added as a polymerization terminator and the reaction was carried out for 10 minutes under a nitrogen atmosphere. Then, a vacuum was gradually applied at 0.5 Torr or lower After reaching the target viscosity, the reaction was terminated to synthesize a polyarylene sulfide resin which did not contain a carboxyl group or an amine group at the end of the main chain. The resin after completion of the reaction was prepared in the form of pellets using a small strand cutter.

Analyzes the polyarylene sulfide resin of this Comparative Example 1 was confirmed by FT-IR, a carboxyl group or an amine group of the N peaks are approximately 1600 to 1800cm ^-1 or 3500cm ^-1 to about 3300 on the spectrum.

[ Example  And Comparative Example : Polyarylene Sulfide system  Preparation of resin composition]

A polyarylene sulfide resin composition having the compositions shown in the following Tables 1 and 2 was prepared by the following method.

Example  1 to 6 and Comparative Example  1 to 4: Polyarylene Sulfide system  Preparation of resin composition

The antioxidant, the PPS resin, the compatibilizing agent and the HDPE were uniformly mixed in advance with a super mixer according to the compositions shown in Tables 1 and 2, and the thus obtained primary composition was extruded through a twin-screw extruder (40 mm extruder, L / Of Hopper.

On the other hand, fillers containing inorganic fillers such as carbon fiber, boron nitride (BN), graphite, zinc sulfide, zinc oxide, and magnesium oxide are weighed according to each composition and uniformly mixed in advance using a super mixer or a blender, Side side of the twin-screw extruder using a primary side feeder. In order to keep the content of inorganic filler constant, an inorganic filler was supplied to a side feeder using a separate metering device and an inorganic filler was injected into a twin screw extruder using a side feeder.

The thus introduced inorganic filler was homogeneously mixed with the first composition by a kneading screw in a twin-screw extruder.

The glass fibers were put into a secondary side feeder, the mixed and volatile gases were removed under reduced pressure, and the heat-generating compound strands were produced in the form of a pellet using a chip cutting machine.

The resin composition of the examples Item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 PPS-1 40 42 42 31.8 30.8 34.8 PPS-2 - - - - - - BN-1 10 7 7 7 10 3 BN-2 22 7 7 7 17 10 BN-3 - - - - - - ZnS 5 15 - 5 10 5 MgO - - 15 - - - ZnO - - - 20 - - Graphite 1 11 17 17 17 5 5 Graphite 2 - - - - 15 30 Graphite 3 - - - - - - Carbon fiber - - - - - - Glass fiber 10 10 10 10 10 10 Compatibilizer 2 2 2 2 2 2 Antioxidant 0.2 0.2 0.2 0.2 0.2 0.2

The resin composition of Comparative Example Item Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 PPS-1 41.8 32.8 32.8 PPS-2 - - - 41.8 BN-1 7 5 - 12 BN-2 7 10 - 15 BN-3 - - - ZnS 15 40 - MgO - - - ZnO - - 35 Graphite 1 - - 20 10 Graphite 2 - - - 15 Graphite 3 17 - - Glass fiber 10 10 10 10    HDPE - - - Compatibilizer 2 2 2 2 Antioxidant 0.2 0.2 0.2 0.2

Each component used in Examples and Comparative Examples Item Characteristics PPS PPS-1 (Synthesis Example 1: MV: 600, terminally substituted), PPS-2 (Synthesis Example 2: MV: BN BN-1 (average particle diameter: 5 占 퐉, non-coating), BN-2 (average particle diameter: 20 占 퐉, stearic acid surface coating) ZnS Average particle diameter: 0.5 to 0.7 탆, ZnS content (96% or more), Mohs hardness: 3 MgO Average particle diameter: 3.5 占 퐉, specific gravity: 3.3, purity not less than 99.6% ZnO Average particle diameter: 0.3 to 0.8 占 퐉, specific gravity: 5.4, purity: 99.5% Graphite G / P-3: Expanded graphite, ash: 0.3%, G / P-2: Expanded graphite, ash: 0.3% Glass Fiber Thickness: 13 탆, length 3 mm HDPE MI: 5 (190 DEG C, 2.16 kg)   Compatibilizer Epoxy silane (molecular weight 278)

[Experimental Example]

The following properties were measured for the resin compositions obtained in the Examples and Comparative Examples. For reference, the following properties are based on the result of preparing each resin composition through a twin-screw extruder and preparing a physical sample and a flat plate sample having a size of about 1.2 mm and measuring the room temperature (23 ° C).

1. Thermal conductivity (ASTM D1461): The thermal capacity and thermal diffusivity of the resin composition samples obtained in the examples and comparative examples were measured using a Netzsch (LFA 427) laser flash device and the density was measured using a mill tool piping The thermal conductivity was then calculated by multiplying the heat capacity, the thermal diffusivity and the density.

2. Volumetric Resistance (Electrical Conductivity) (ASTM D257): Electrical conductivity of each resin composition sample was measured by measuring the volume resistance according to ASTM D257.

In general, 10 ¹² Ωcm is insulation type (not electrically conductive), and when it is less than 10 ⁶ Ωcm, it can be referred to as conduction type (electrically conductive) material.

Volume Resistance (Ωcm) is the intrinsic resistance of a given pure material, taking into account the resistance and area of the measuring surface and the thickness of the object. Electrodes were placed on the top and bottom of a flat plate of a certain thickness, and the resistance was measured and found by the following equation.

Volume resistivity (rho v) = A / t ˙Rm (Ω cm)

A: contact sectional area (cm 2) of the electrode, t: thickness (cm) of the measured object, Rm:

3. Tensile strength: The tensile strengths of the resin composition samples obtained in Examples and Comparative Examples were measured according to the ASTM D 638 method.

4. Impact strength (Izod): The impact strength of the resin composition samples obtained in Examples and Comparative Examples was measured according to the ASTM D 256 method

The following measurement results are shown in Tables 4 and 5.

Experimental results on the resin composition of the examples Item unit Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Thermal conductivity   W / mK 6.7 6.2 5.8 6.0 8.8 10.2 Electric conduction Ohm.cm 1.5E + 13 1.2E + 13 1.1E + 13 1.1E + 13 1.0E + 14 1.0E + 3 The tensile strength kgf / cm ² 800 950 830 750 1050 1130 Impact strength J / m 54 52 53 58 53 52 TYPE Isolation Isolation Isolation Isolation Isolation Isolation COLOR BLACK BLACK BLACK BLACK BLACK BLACK

Experimental results on the resin composition of Comparative Example Item unit Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Thermal conductivity  W / mK 2.5 1.8 2.7 3.1 Electric conduction Ohm.cm 1.0E + 5 1.0E + 12 1.0E + 12 1.0E + 12 The tensile strength kgf / cm2 620 420 420 515 Impact strength J / m 32 28 29 28 TYPE Evangelize Isolation Isolation Isolation COLOR BLACK WHITE BLACK BLACK

Referring to Table 4, the resin compositions of Examples 1 to 6 including three kinds of inorganic fillers together with the PPS having a predetermined reactive group introduced thereto are superior in thermal conductivity, particularly, in a high heat-dissipating plastic of 5 W / mK or more Which is suitable to be used in the present invention. It has also been confirmed that such a resin composition has a thermally conductive property of an insulating type exhibiting excellent properties in terms of mechanical properties such as tensile strength and impact strength.

The excellent physical properties of Examples 1 to 6 are believed to be due to the synergism caused by the use of three kinds of the inorganic fillers, and furthermore, the use of the PPS having a reactive group having excellent compatibility with the inorganic filler do. Further, it is predicted that the use of two or more kinds of surface-coated boron nitride having different average particle diameters together can realize more excellent physical properties.

In contrast, in the case of Comparative Example 1 using natural graphite instead of expandable graphite and Comparative Examples 2 and 3 containing no expanded graphite or boron nitride, the total content of the inorganic filler was in the range similar to the embodiment It was confirmed that the thermal conductivity and the mechanical properties were poor. Also, it was confirmed that the resin composition of Comparative Example 4 containing no zinc sulfide, magnesium oxide and zinc oxide also had poor thermal conductivity and mechanical properties.

Claims (21)

Polyarylene sulfide,
Expandable graphite; Boron nitride; And an inorganic filler containing at least one selected from the group consisting of zinc sulfide, magnesium oxide and zinc oxide,
Wherein at least one of the inorganic fillers has an organic coating-treated surface.
The polyarylene sulfide resin composition according to claim 1, wherein the polyarylene sulfide comprises a disulfide repeating unit in the repeating unit of the main chain.
3. The polyarylene sulfide resin composition according to claim 2, wherein the disulfide repeating unit is contained in an amount of 3% by weight or less based on the total polyarylene sulfide.
The polyarylene sulfide resin composition according to claim 1, wherein the polyarylene sulfide has a number average molecular weight of 5,000 to 50,000.
The polyarylene sulfide-based resin composition according to claim 1, wherein the polyarylene sulfide has a melt viscosity of 10 to 50,000 poise measured at 300 캜 by a rotating disk viscometer.
The polyarylene sulfide resin composition according to claim 1, wherein a carboxyl group (-COOH) or an amine group (-NH ₂ ) is introduced into at least a part of the end group of the polyarylene sulfide main chain.
The polyarylene sulfide-based resin composition according to claim 6, wherein the polyarylene sulfide exhibits a peak of 1600 to 1800 cm ^-1 or 3300 to 3500 cm ^-1 on the FT-IR spectrum.
The polyarylene sulfide resin composition according to claim 1, wherein the inorganic filler is structurally connected to each other in surface contact with each other in polyarylene sulfide.
The polyarylene sulfide resin composition according to claim 1, wherein the boron nitride has an organic coating surface.
The polyarylene sulfide resin composition according to claim 1, wherein the expanded graphite comprises at least one expanded graphite having an average particle diameter of 1 to 1000 mu m and an aspect ratio of 50 or more.
The polyarylene sulfide resin composition according to claim 1, wherein the expanded graphite has a hexagonal crystal structure.
The polyarylene sulfide resin composition according to claim 1, wherein the boron nitride comprises at least one hexagonal boron nitride having an average particle diameter of 5 to 1000 占 퐉 and an aspect ratio of 50 to 300.
13. The polyarylene sulfide resin composition according to claim 12, wherein the boron nitride comprises two or more kinds of boron nitride having different average particle sizes.
The method according to claim 1,
10 to 80% by weight of polyarylene sulfide,
1 to 50% by weight of expanded graphite,
1 to 50% by weight of boron nitride, and
1 to 50% by weight of at least one selected from the group consisting of zinc sulfide, magnesium oxide and zinc oxide.
The polyarylene sulfide resin composition according to claim 1, further comprising a thermoplastic resin, a thermoplastic elastomer or a filler.
2. The composition of claim 1, wherein the silane compound, maleic anhydride, titanate, zirconate, fumaric acid, phosphate, stearic acid, 0.1 to 20% by weight of at least one compatibilizing agent selected from the group consisting of a metal stearate and a wax is further contained in the polyarylene sulfide based resin composition.
The polyarylene sulfide resin composition according to claim 1, further comprising 1 to 50% by weight of glass fiber.
The polyarylene sulfide resin composition according to claim 17, wherein the glass fiber has an average particle diameter of 2 to 5 mm and a thickness of 10 to 15 탆.
A molded article comprising the polyarylene sulfide resin composition of claim 1.
20. A shaped article according to claim 19 in the form of a film, sheet or fiber.
The molded article as claimed in claim 19, which is used as an automobile interior part, an automobile exterior part, an electric part, an electronic part or an industrial material.